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  • 1
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    Heme b in marine phytoplankton and particulate material from the North Atlantic Ocean (2013)
    Inter Research
    In:  Marine Ecology Progress Series, 483 . pp. 1-17.
    Details
    Publication Date: 2017-10-24
    Description: Concentrations of heme b, the ironcontaining prosthetic group of many hemoproteins, were measured in 6 species of marine phytoplankton (Dunaliella tertiolecta, Emiliania huxleyi, Thalassio - sira weissflogii, T. oceanica, Phaeodactylum tricor - nutum and Synechococcus sp. WH7803) that were subjected to variations in iron concentration. Changes in heme b in response to reduced light and nitrate were also ex amined for E. huxleyi and T. oceanica. Results from laboratory cultures were compared with heme b determined in particulate material in the North Atlantic. In cultures, heme b made up 18 ± 14% (SE) of the total iron pool. Reduced iron and nitrate concentrations resulted in a decreased intracellular heme b concentration, expressed as per mole carbon. Chlorophyll a (chl a) to heme b ratios in E. huxleyi and D. tertiolecta in creased in response to limited light and nutrient availability, but slightly decreased or did not change in the diatoms and the cyanophyte Synechococcus sp. WH7803. The heme b:particulate organic carbon (POC) and chl a:heme b ratios in the North Atlantic were within the range observed in phytoplankton cultures. In the surface mixed layer, decreases in heme b:POC ratios were linked to decreases in nutrient concentrations. Chl a:heme b ratios increased with depth and were thus primarily affected by light availability. Relative relationships between heme b, chl a and POC in the North Atlantic likely represented a change in the ability of cells to undertake cellular processes driven by chl a (light harvesting) and heme b (e.g. electron transport) according to ambient light and nutrient conditions.
    Type: Article , PeerReviewed
    Format: text
    DOI: 10.3354/meps10367
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  • 2
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    Heme b quotas are low in Southern Ocean phytoplankton (2015)
    Inter Research
    In:  Marine Ecology Progress Series, 532 . pp. 29-40.
    Details
    Publication Date: 2021-04-23
    Description: Heme is the iron-containing prosthetic group of hemoproteins, and is thus required for photosynthesis, respiration and nitrate reduction in marine phytoplankton. Here we report concentrations of heme b in Southern Ocean phytoplankton and contrast our findings with those in coastal species. The concentration of particulate heme b (pmol l-1) observed at the end of the exponential growth phase was related to the concentration of dissolved iron in the culture media. Small Southern Ocean phytoplankton species (〈6 μm in diameter) had heme b quotas 〈1 μmol mol-1 carbon, the lowest yet reported for marine phytoplankton. Heme b was also depleted in these species with respect to chlorophyll a. We calculated the amount of carbon accumulated per mole of heme b per second in our cultures (heme growth efficiency, HGE) and found that small Southern Ocean species can maintain growth rates, even while heme b content is reduced. Small Southern Ocean phytoplankton can thus produce more particulate carbon than larger Southern Ocean or small coastal species at equivalent iron concentrations. Combining primary productivity and heme b concentrations reported for the open ocean, we found that HGE in natural populations was within the range of our laboratory culture results. HGE was also observed to be higher at open ocean stations characterized by low iron concentrations. Our results suggest that low heme b quotas do not necessarily result in reduced growth and that marine phytoplankton can optimize iron use by manipulating the intracellular hemoprotein pool
    Type: Article , PeerReviewed
    Format: text
    DOI: 10.3354/meps11345
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  • 3
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    Stoichiometry of Fe, Mn and Co in the marine diazotroph Crocosphaera subtropica ATCC51142 in Fe- and P-limited continuous cultures (2020)
    Inter Research
    Details
    Publication Date: 2023-02-08
    Description: We investigated trace element stoichiometries of the nitrogen-fixing marine cyanobacterium Crocosphaera subtropica ATCC51142 under steady-state growth conditions. We utilized exponentially fed batch cultures and varied iron (Fe) concentrations to establish nutrient limitation in C. subtropica growing at a constant growth rate (0.11 d -1 ). No statistical difference in cell density, chlorophyll a , particulate organic carbon (C), nitrogen (N) and phosphorus (P) were observed between consecutive days after Day 14, and cultures were assumed to be at steady state with respect to growth for the remaining 11 d of the experiment. Cultures were limited by P in the highest Fe treatment (41 nmol l -1 ) and by Fe in the 2 lower-concentration Fe treatments (1 and 5 nmol l -1 ). Cell size and in vivo fluorescence changed throughout the experiment in the 1 nmol l -1 Fe treatment, suggesting ongoing acclimation of C. subtropica to our lowest Fe supply. Nevertheless, Fe:C ratios were not significantly different between the Fe treatments, and we calculated an average (±SD) Fe:C ratio of 32 ± 14 µmol mol -1 for growth at 0.11 d -1 . Steady-state P-limited cells had lower P quotas, whilst Fe-limited cells had higher manganese (Mn) and cobalt (Co) quotas. We attribute the increase in Mn and Co quotas at low Fe to a competitive effect resulting from changes in the supply ratio of trace elements. Such an effect has implications for variability in elemental stoichiometry in marine phytoplankton, and potential consequences for trace metal uptake and cycling in marine systems.
    Type: Article , PeerReviewed
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  • 4
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    In situ measurements of explosive compound dissolution fluxes from exposed munition material in the Baltic Sea (2019)
    ACS (American Chemical Society)
    In:  Environmental Science & Technology, 53 (10). pp. 5652-5660.
    Details
    Publication Date: 2022-01-31
    Description: Underwater munitions containing millions of tons of toxic explosives are present worldwide in coastal marine waters as a result of unexploded ordnance and intentional dumping. Dissolution flux of solid explosives following corrosion of metal munition housings controls exposure of biological receptors to toxic munition compounds (MC; including TNT: 2,4,6-Trinitrotoluene, RDX: 1,3,5-Trinitro-1,3,5-triazinane, and DNB: 1,3-Dinitrobenzene). Very little is known about the dissolution behavior of MC in the marine environment. In this work, we exploit a unique marine study site in the Baltic Sea with exposed solid explosives to quantify in situ MC dissolution fluxes using dissolved MC gradients near the exposed explosive surface, as well as benthic chamber incubations. The gradient method gave dissolution fluxes that ranged between 0.001 and 3.2, 0.0001 and 0.04, and 0.003 and 1.7 mg cm-2 d-1 for TNT, RDX, and DNB, respectively. Benthic chamber incubations indicated dissolution fluxes of 0.0047-0.277, 0-0.11, and 0.00047-1.45 mg cm-2 d-1 for TNT, RDX, and DNB, respectively. In situ dissolution fluxes estimated in the current study were lower than most dissolution rates reported for laboratory experiments, but clearly demonstrated that MC are released from underwater munitions to the water column in the Baltic Sea.
    Type: Article , PeerReviewed
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    DOI: 10.1021/acs.est.8b06974
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  • 5
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    Seasonal Variations in Proton Binding Characteristics of Dissolved Organic Matter Isolated from the Southwest Baltic Sea (2021)
    ACS (American Chemical Society)
    Details
    Publication Date: 2024-02-07
    Description: The physicochemical characteristics of dissolved organic matter (DOM) strongly influence its interactions with inorganic species such as protons and trace elements in natural waters. We collected water samples at Boknis Eck, a time series station in the Baltic Sea with a low exposure to freshwater inputs, to investigate how seasonal fluctuations impact the proton binding properties of the isolated DOM. We used potentiometric titrations to assess the binding properties of solid-phase extracted DOM (SPE–DOM) over a seasonal cycle. We report and critically analyze the first NICA parameters estimates of carboxylic-like and phenolic-like sites for brackish water SPE–DOM. The total amount of functional groups (QmaxH,tot) showed no seasonal fluctuations and an average value of 136 ± 5.2 mmol·mol C–1. The average proton affinity (logKH) and binding site heterogeneity (m) showed a relatively minor variability for samples obtained between April and September, when the water remained stratified. These results contribute to a better understanding of the ion binding characteristics of DOM in natural brackish waters.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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    Format: archive
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  • 6
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    Influence of pH and Dissolved Organic Matter on Iron Speciation and Apparent Iron Solubility in the Peruvian Shelf and Slope Region (2021)
    ACS (American Chemical Society)
    Details
    Publication Date: 2024-02-07
    Description: The chemical speciation of iron (Fe) in oceans is influenced by ambient pH, dissolved oxygen, and the concentrations and strengths of the binding sites of dissolved organic matter (DOM). Here, we derived new nonideal competitive adsorption (NICA) constants for Fe(III) binding to marine DOM via pH-Fe titrations. We used the constants to calculate Fe(III) speciation and derive the apparent Fe(III) solubility (SFe(III)app) in the ambient water column across the Peruvian shelf and slope region. We define SFe(III)app as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). A ca. twofold increase in SFe(III)app in the oxygen minimum zone (OMZ) compared to surface waters is predicted. The increase results from a one order of magnitude decrease in H+ concentration which impacts both Fe(III) hydroxide solubility and organic complexation. A correlation matrix suggests that changes in pH have a larger impact on SFe(III)app and Fe(III) speciation than DOM in this region. Using Fe(II) measurements, we calculated ambient DFe(III) and compared the value with the predicted SFe(III)app. The underlying distribution of ambient DFe(III) largely reflected the predicted SFe(III)app, indicating that decreased pH as a result of OMZ intensification and ocean acidification may increase SFe(III)app with potential impacts on surface DFe inventories.
    Type: Article , PeerReviewed
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  • 7
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    Proton Binding Characteristics of Dissolved Organic Matter Extracted from the North Atlantic (2023)
    ACS (American Chemical Society)
    Details
    Publication Date: 2024-02-07
    Description: Marine dissolved organic matter (DOM) presents key thermodynamic properties that are not yet fully constrained. Here, we report the distribution of binding sites occupied by protons (i.e., proton affinity spectra) and parametrize the median intrinsic proton binding affinities (log K̅H) and heterogeneities (m), for DOM samples extracted from the North Atlantic. We estimate that 11.4 ± 0.6% of C atoms in the extracted marine DOM have a functional group with a binding site for ionic species. The log K̅H of the most acidic groups was larger (4.01–4.02 ± 0.02) than that observed in DOM from coastal waters (3.82 ± 0.02), while the chemical binding heterogeneity parameter increased with depth to values (m1= 0.666 ± 0.009) ca. 10% higher than those observed in surface open ocean or coastal samples. On the contrary, the log K̅H for the less acidic groups shows a difference between the surface (10.01 ± 0.08) and deep (9.22 ± 0.35) samples. The latter chemical groups were more heterogeneous for marine than for terrestrial DOM, and m2 decreased with depth to values of 0.28 ± 0.03. Binding heterogeneity reflects aromatic carbon compounds’ persistence and accumulation in diverse, low-abundance chemical forms, while easily degradable low-affinity groups accumulate more uniformly in the deep ocean.
    Type: Article , PeerReviewed
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  • 8
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    Rapid, At-Sea Detection of Munition Compounds in Coastal Waters Using a Shipboard System (2023)
    ACS (American Chemical Society)
    Details
    Publication Date: 2024-02-29
    Description: Coastal waters are contaminated globally with millions of metric tons of munitions from the two world wars which constitute a potential threat to ecosystems and humans. Laboratory-based chemical methods for the detection of munition compounds (MCs) in seawater typically take weeks to months between sample collection and analysis. The current work details a novel, field-deployable system for rapid (under 10 min) analysis of four common MCs (1,3-dinitrobenzene (DNB), amino-4,6-dinitrotoluene (ADNT), 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)). The system uses a fluidic preconcentration unit with high-performance liquid chromatography (HPLC) and detection by electrospray-ionization mass spectrometry and UV–vis spectroscopy. The fluidic unit comprises two solid-phase extraction (SPE) columns for preconcentration of target MCs from the seawater matrix and allows loading and analysis of two samples simultaneously. Seven SPE resins were tested for extraction efficiency and robustness, with Porapak RDX showing best performance. Chromatographic separation of target MCs was performed using a C8 reversed-phase HPLC column. Limits of detection (LODs) were 3.7, 1.8, 3.6, and 10.7 ng L–1 for DNB, ADNT, TNT, and RDX, respectively. The system’s analytical performance and automated data processing procedure were demonstrated in the Baltic Sea.
    Type: Article , PeerReviewed
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